Quaternary ammonium organotin halides



United States Patent 3,346,607 QUATERNARY AMMONIUM ORGANOTIN HALIDES Michael E. Lombardo, Nanuet, N.Y., assignor to stapling Machines C0., Rockaway, N.J., a corporation of Delaware No Drawing. Filed Dec. 29, 1964, Ser. No. 422,033

11 Claims. (Cl. Z60-429.7)

ABSTRACT OF THE DISCLOSURE in each of which x+m+n is about 10.

This invention relates to certain organotin compounds, and relates in particular to quaternary ammonium salts formed between "certain organotin halides and certain tertiary amines.

US. Patent 3,037,039, granted May 29, 1962 to Mazur, discloses the reaction of organotin halides such as trialkyltin halides with secondary amine materials having an N-substituted long chain fatty hydrocarbon radical and an N-substituted polyoxyethylene chain. The materials formed by the reaction of the organotin halides with the secondary amines are taught to be germicidal and fungicidal.

The applicant has now discovered that by reacting certain organotin halides with tertiary amine materials having a long chain fatty hydrocarbon portion and two or more polyoxyethylene residues, new compounds with surprisinglyimproved properties are obtained.

- Most importantly, the new compounds of the present invention show a much more pronounced biological activity than do the compounds known in the prior art. Further, the materials of the invention are more soluble in water than are the materials of the prior art. This facilitates their application from solution and their use in high concentrations. Also, the reaction products formed between tertiary amines and organotin halides according to the present invention are quaternary ammonium salts, unlike the tertiary amines formed between secondary amines and organotin halides as in the prior art. In certain applications, for example the impregnation of wood with fungicides to render it resistant to the growth of molds and other fungi, the electrically charged salts of the present invention are much more tenaciously'held by the treated material than are the electrically neutral compounds of the prior art. Thus, the compounds of the present invention give minimum leaching out when used for impregnating wood. Problems of leaching can be of critical importance if the wood (or another treated substrate) is employed for the packaging of food, in which case it is desirable to have as little transfer as possible of the fungicide or germicide from the treated packaging materials to the contents of the package.

One class of compounds according to the present invention has the formula wherein Hal is a halide anion, R is a long chain fatty hydrocarbon radical, and the subscripts x-l-y total about ten or about fifty. Attached ot the tin atom of these compounds is a lower alkyl radical, R, having up to six carbon atoms, preferably one having three or four carbon atoms such as propyl, isopropyl, buytl, t-butyl, isobutyl,

etc.

These compounds are conveniently formed between a tri-alkyltin halide (usually the chloride since it is the cheapest commercial product, but use of the fluoride, bromide or iodide is also contemplated), with a polyoxyethylated amine. The amines are available commercially and are formed by the condensation of ethylene oxide with a fatty amine material. Generally the hydrocarbon portion of the fatty amine contains from 12 to 18 carbon atoms, and includes mixed. saturated and unsaturated hydrocarbons such as stearyl, palmityl, and oleyl amine residues.

The reaction between the tri-alkyltin compound and the amine can be carried out by contacting the compounds, preferably by refiuxing at temperatures from C. to C. with or without an inert solvent present. At temperatures much in excess of 150 C., decomposition of the reactants or products may occur. Below about 120 C., the reaction is inconveniently slow. The reaction is carried out under reflux in view of the volatility of the tin halide reagents. Alcohols such as isopropyl alcohols are convenient solvents indifferent or inert to the reagents and products, but their use is not critical and equivalent solvents can be employed.

Another preferred class of compounds formed according to the present invention is formed by reacting a trialkyltin halide, preferably the chloride, with a di-amine of the formula RNoH,oHoH,-N

(CH2CH20)zH where R is a long chain fatty hydrocarbon residue and x+y+z is about 10. When approximately equimolar quantities of the tin compound and di-amine are reacted, the tin may attach to either of the nitrogen atoms, so that a mixture of compounds of the formulas CHZCHZO) an.

and

(omomonH onzornm n RNCHzCHzCHz-N-S11(R) Hal- (omomo) .H

is formed. The mixture can be separated into its components chromatographically, but is generally empolyed in germicidal and fungicidal compositions without separation. x

When approximately two moles of tin halide are reacted per mole of (ii-amine, compounds having two atoms of tin in the final product are produced, corresponding with the formula where x+y+z is about 10. These compounds are of particular interest because of their high fungicidal and germicidal activity. They are prepared as discussed earlier herein, namely either the reagent amine and tri-alkyltin halides are contacted in bulk or in a solvent at elevated temperatures.

As mentioned earlier herein, the compounds of the present invention have strikingly good biocidal properties. Accordingly, they can be employed as germicides and fungicides in the many uses suggested in the prior art for compounds formed between secondary amines and tin halides. However, the compounds of the invention have particular utility in the treatment of wood used in the manufacture of crates and boxes to discourage the formation of discoloring fungus growths on the wood.

A better understanding of the present invention will be had by referring to the following specific examples given by way of illustration.

Example 1 Stearyl tri n propyltin di polyoxyethylene ammonium chloride was formed by adding 28.3 grams of tri n propyltin chloride to 71.0 grams (0.1 mole) of a di polyoxyethylated stearyl amine of the formula (CHQCHZOMH CisHavN (CH2CH20) H Where x+y is about 10. The reaction mixture was heated under reflux to a temperature of 121 C. over a 60 minute period. The product is an amber colored liquid with a specific gravity at 25 C.=1.0577. Titration of the quaternary ammonium ion demonstrated a 96.5% yield of the stearyl tri n propyltin di polyoxyethylated ammonium chloride. Analysis for tin gave 12.10%, as compared with 11.95'% for C H O NClSn.

Example 2 Stearyl tri n butyltin di polyoxyethylene ammonium chloride was formed by adding 32.6 grams (0.1 mole) of tri n butyltin chloride to 71.0 grams (0.1 mole) of the di polyoxyethylated stearyl amine of Example 1 in 34.5 grams of isopropyl alcohol. The mixture was refluxed for 16 hours. Titration of the quaternary ammonium ion showed a yield of 84.1% of stearyl tri nbutyltin di polyoxyethylene ammonium chloride.

Example 3 Stearyl tri n propyltin di polyoxyethylene ammonium chloride was formed by adding 8.5 grams (0.03 mole) of tri n propyltin chloride to 74.1 grams (0.03 mole) of a di polyoxyethylated stearyl amine of the formula where x+y is about 50. The reaction mixture was heated under reflux to a temperature of 151 C. over a 64 minute period. The product is an amber waxy solid. Titration of the quaternary ammonium ion demonstrated a 93.5% yield of the stearyl tri n propyltin di polyoxyethylated ammonium chloride. Analysis for tin gave 4.59%, as compared with 4.31% for C H O NClSn.

Example 4 Stearyl tri n butyltin di polyoxyethylene ammonium chloride was formed by adding 9.8 grams (0.03 mole) of tri n butyltin chloride to 74.1 grams (0.03 mole) of the di po-lyoxyethylated stearyl amine of Example 3 in 28.0 grams of isopropyl alcohol. The reaction mixture was refluxed for 16 hours. Titration of the quaternary ammonium ion showed a 94.3% yield of the stearyl trin butyltin di polyoxyethylene ammonium chloride salt.

Example 5 A mixture of the two tri n propyltin ammonium chlorides of a tri polyoxyethylated N alkyl trimethylene diamine was prepared by adding 28.3 grams (0.1 mole) of tri n propyltin chloride to 86.0 grams (0.1 mole) of a tallow amine of the formula (CHzCHzO)xH (OI-IzCH2O) H RN--CH2CH2CH2N (OHzGHzOhH where x+y+z is about 10. The reactants were heated with agitation under reflux to a temperature of 136 C. over a 60 minute period. The product is a reddish brown liquid having a specific gravity at 25 C.=1.0685. Titration of the quaternary ammonium ion showed a 97.64% yield. Analysis for tin showed 10.42% as compared with 10.38% for a mixture of quaternary ammonium salts having an average molecular weight of 1143.415.

Example 6 A bis (tri n propyltin) diam-monium chloride of a tri polyoxyethylated N alkyl trimethylene diamine was prepared by adding 56.7 grams (0.2 mole) to 86.0 grams (0.1 mole) of tri n propyltin chloride of a tallow amine of the formula (CHzCHzO) H CH2OH20) ,H

where x+y+z is about 10. The mixture was heated with agitation under reflux to a temperature of C. for 75 minutes. The product is a reddish brown liquid having a specific gravity at 25 C.=1.1093. Titration of the quaternary ammonium ion showed a yield of 97.3%. Analysis for tin gave 16.79% as compared with 16.64% for the diammonium chloride having an average molecular weight of 1426.83.

j| Haland x-I-m-l-n is about 10; (1)) wherein R is a long chain fatty hydrocarbon, R"

x+p+q is about 10, and R is lower alkyl; and

wherein Hal is a halide ion, R is a long chain fatty hydrocarbon, R is lower alkyl, and x+y is about 10.

3. A compound as in claim 2 wherein R is --C18H37 and R is -C3HI1.

4. A compound of the formula wherein Hal is a halide ion, R is a long chain fatty hydrocarbon, R is lower alkyl, and x+z is about 50.

5. A compound as in claim 4 wherein R is -C18H37 and R is -C H 6. A compound of the formula wherein Hal is a halide ion, R is a long chain fatty hydrocarbon, R is lower alkyl, and x+m +n is about 10. 7. A compound as in claim 6 wherein R is a tallow hydrocarbon and R is -C H-;.

wherein Hal is a halide ion, R is a long chain fatty hydrocarbon, R is lower alkyl, and x+p+q is about 10. 9. A compound as in claim 8 wherein R is a tallow hydrocarbon and R is --C H 10. A compound of the formula (CHiCHzOhH (CHzCHzOhH (R)3S,1NCHiCHzCHr-N-R Halwherein Hal is a halide ion, R is lower alkyl, R is a long chain fatty hydrocarbon, and x+r+s is about 10.

11. A compound as in claim 10 wherein R is a tallow hydrocarbon and R is -C H References Cited UNITED STATES PATENTS 3,037,039 5/1962 Mazur 260429.7 X

TOBIAS E. LEVOW, Primary Examiner.

HELEN M. McCARTI-IY, Examiner.

W. F. W. BELLAMY, Assistant Examiner. 

1. A COMPOUND OF THE FORMULA 